Probing the Interfacial Properties of Oil-Water Interfaces Decorated with Ionizable, pH Responsive Silica Nanoparticles.

Abstract

Particle-stabilized emulsions (Pickering emulsions) have recently attracted significant attention in scientific studies and for technological applications. The interest stems from the ease of directly assembling the particles at interfaces and modulating the interfacial properties. In this paper, we demonstrate the formation of stable, practical emulsions leveraging the assembly of ionizable, pH responsive silica nanoparticles, surface-functionalized by a mixture of silanes containing amine/ammonium groups, which renders them positively charged. Using pH as the trigger, the assembly and the behavior of the emulsion are controlled by modulating the charges of the functional groups of the nanoparticle and the oil (crude oil). In addition to their tunable charge, the particular combination of silane coupling agents leads to stable particle dispersions, which is critical for practical applications. Atomic force microscopy and interfacial tension (IFT) measurements are used to monitor the assembly, which is controlled by both the electrostatic interactions between the particles and oil and the interparticle interactions, both of which are modulated by pH. Under acidic conditions, when the surfaces of the oil and the nanoparticles (NPs) are positively charged, the NPs are not attracted at the interface and there is no significant reduction in the IFT. In contrast, under basic conditions in which the oil carries a high negative charge and the amine groups on the silica are deprotonated while still positively charged because of the ammonium groups, the NPs assemble at the interface in a closely packed configuration yielding a jammed state with a high dilatational modulus. As a result, two oil droplets do not coalesce even when pushed against each other and the emulsion stability improves significantly. The study provides new insights into the directed assembly of nanoparticles at fluid interfaces relevant to several applications, including environmental remediation, catalysis, drug delivery, food technology, and oil recovery.